CN112023726B - Low-energy-consumption high-flux reverse osmosis membrane and preparation method and application thereof - Google Patents
Low-energy-consumption high-flux reverse osmosis membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN112023726B CN112023726B CN202010794089.9A CN202010794089A CN112023726B CN 112023726 B CN112023726 B CN 112023726B CN 202010794089 A CN202010794089 A CN 202010794089A CN 112023726 B CN112023726 B CN 112023726B
- Authority
- CN
- China
- Prior art keywords
- reverse osmosis
- osmosis membrane
- phase solution
- sulfonate
- flux
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a reverse osmosis membrane with low energy consumption and high flux as well as a preparation method and application thereof. The reverse osmosis membrane provided by the invention has the characteristics of low energy consumption, high hydrophilicity, high water yield and the like, and can be widely applied to the water treatment fields of industrial water supply, wastewater reuse and the like.
Description
Technical Field
The invention relates to the technical field of water treatment materials, in particular to a reverse osmosis membrane with low energy consumption and high flux as well as a preparation method and application thereof.
Background
Nowadays, with the industrial development and the population explosion, the problem of increasingly short water resources is more and more aroused attention of people, and membrane separation, especially reverse osmosis membrane technology, has been widely applied to the water treatment fields such as seawater and brackish water desalination, wastewater reuse and the like due to the characteristics of high separation efficiency, low energy consumption, less pollution and the like.
The current mainstream commercial reverse osmosis membrane in the market is an aromatic polyamide reverse osmosis composite membrane invented by Dow Filmtec company in 1981, the reverse osmosis membrane utilizes m-phenylenediamine and trimesoyl chloride to carry out interfacial polycondensation reaction on the surface of a polysulfone support membrane to form a polyamide desalination layer, and the polyamide layer is the key for influencing water permeability and salt retardation. Therefore, it has been the subject of many researchers to optimize a polyamide layer in order to obtain a reverse osmosis membrane having a large flux and a high salt rejection rate by focusing attention on an interfacial polycondensation reaction.
The reverse osmosis membrane with low energy consumption and high flux has low energy consumption, can effectively save investment and equipment operation cost, and improves the treatment efficiency. The patents and literature published so far have mainly developed studies around the optimization of porous support membranes and the optimization of polyamide layers. In particular, the optimization of the polyamide layer is researched more, and the addition of different types of additives into the aqueous solution or the organic solution is mostly focused on influencing the interfacial polycondensation process to improve the structure of the polyamide layer to improve the flux. For example, U.S. Pat. Nos. 5,5254261 and 6171497 disclose a method for increasing water flux of composite membranes by adding amine salt and isopropanol into polyamine aqueous phase solution; US patent US687827 enhances water flux by adding a phosphorus-containing complexing agent to the organic phase solution. Besides adding small organic molecules into the aqueous phase or organic phase solution, the addition of inorganic nanoparticles can also achieve the improvement of water flux. Patent CN101791522 discloses a hybrid reverse osmosis membrane composite membrane of carbon nanotubes, which greatly improves the flux of the membrane while maintaining the desalination rate of the reverse osmosis membrane by adding carbon nanotubes into aqueous phase or organic phase solution. Similarly, patent CN111266017A and patent CN105080358 disclose that a substantial increase in water flux is achieved by doping modified graphene oxide and attapulgite during interfacial polymerization.
Although some technical solutions for improving the water flux of the reverse osmosis membrane have been formed in the prior art, the technical solutions have certain problems in the application process. If a small molecular organic matter is added in the interfacial polymerization process, although the flux can be improved, the salt rejection rate is seriously reduced; the problems of large preparation difficulty, easy shedding in later period and the like when the inorganic nano particles are used on a large scale limit the industrial application of the inorganic nano particles. Therefore, a simple and feasible technical scheme capable of improving the water flux of the reverse osmosis membrane on the premise of keeping the desalination rate to be reduced to a small degree is needed.
Disclosure of Invention
The inventors of the present invention have unexpectedly found that, in the interfacial polycondensation reaction between m-phenylenediamine and trimesoyl chloride, when a mixture of a hydroxysulfonate and an alkanolamine is added to an aqueous solution of m-phenylenediamine, a reverse osmosis membrane prepared has the characteristics of high hydrophilicity and high yield while maintaining a high salt removal rate, thereby completing the present invention.
The invention aims to provide a reverse osmosis membrane with low energy consumption and high flux, which can greatly improve the water flux of the reverse osmosis membrane on the premise of keeping the salt rejection rate to be reduced to a small extent.
The invention also aims to provide a simple and feasible preparation method of the reverse osmosis membrane with low energy consumption and high flux.
The invention further aims to provide application of the reverse osmosis membrane with low energy consumption and high flux in the field of water treatment.
The invention is realized by the following technical scheme:
a low energy consumption high flux reverse osmosis membrane comprising a polysulfone porous support layer and a polyamide desalination layer formed on the porous support layer, wherein the polyamide desalination layer contains a mixture of a hydroxy sulfonate and an alcohol amine in or on the surface thereof.
In a specific embodiment, the hydroxy sulfonate is an aliphatic hydroxy sulfonate or an aromatic hydroxy sulfonate; preferably, the hydroxy sulfonate is one or more of hydroxymethyl sodium sulfonate, hydroxyethyl sodium sulfonate, 3-hydroxy-1-propane sodium sulfonate, 4-hydroxybutane sodium sulfonate, sodium p-hydroxybenzene sulfonate dihydrate, 1, 4-dihydroxy-1, 4-butane disulfonate disodium salt, 2, 7-dihydroxy naphthalene-3, 6-disulfonate sodium, 2, 3-dihydroxy naphthalene-6-sulfonate sodium, 1, 2-dihydroxy benzene-3, 5-disulfonate sodium and 2, 5-dihydroxy benzene sulfonic acid potassium.
In a specific embodiment, the alcohol amine is a small molecule alcohol amine; preferably, the small-molecule alcohol amine is one or more of monoethanolamine, diethanolamine, methyldiethanolamine and isopropanolamine, and is more preferably isopropanolamine.
In a specific embodiment, the polyamide desalting layer is formed by performing interfacial polycondensation on an m-phenylenediamine aqueous phase solution and a trimesoyl chloride organic phase solution to form a crosslinked aromatic polyamide with a three-dimensional network structure; the polysulfone porous support layer is a polysulfone support membrane formed on a non-woven fabric.
In another aspect of the present invention, the preparation method of the low energy consumption and high flux reverse osmosis membrane is characterized by comprising the following steps:
1) dissolving m-phenylenediamine aqueous phase solution, hydroxyl sulfonate and alcohol amine blend in water;
2) after the polysulfone porous supporting layer is contacted with the aqueous phase solution, removing the redundant aqueous phase, and then contacting with the trimesoyl chloride organic phase solution;
3) m-phenylenediamine and trimesoyl chloride are subjected to interfacial polycondensation reaction to form a polyamide desalting layer doped with a mixture of hydroxyl sulfonate and alcoholamine on the polysulfone porous supporting layer, and then heat treatment and rinsing are carried out to obtain the reverse osmosis membrane.
In a specific embodiment, the mass concentration of the m-phenylenediamine in the aqueous phase solution in the step 1) is 1.5-3.5 wt%; the mass percentage of the hydroxyl sulfonate is 0.5-2 percent, and the mass percentage of the alcohol amine is 0.01-0.1 percent
In a specific embodiment, the mass concentration of the trimesoyl chloride organic phase solution in the step 2) is 0.06wt% to 0.2 wt%; the organic phase solution is one or more of aliphatic alkane, aromatic alkane and halogenated alkane; aliphatic alkanes are preferred, and isopar G, isopar L and isopar H are more preferred.
In a specific embodiment, the trimesoyl chloride organic phase solution also contains tributyl phosphate with the mass fraction of 0.07-0.25 wt%, based on the mass of the trimesoyl chloride organic phase solution.
In a specific embodiment, the contact time of the polysulfone porous supporting layer in the step 2) with the m-phenylenediamine aqueous phase solution and the trimesoyl chloride organic phase solution is 10-300s, preferably 30-60 s.
In a specific embodiment, said heat treatment in said step 3) is carried out in hot air; the temperature of the hot air is 70-120 ℃, and preferably 90-100 ℃; the heat treatment time is 2-15 min, preferably 3-6 min.
In yet another aspect of the present invention, a reverse osmosis membrane as hereinbefore described or prepared by a process as hereinbefore described is used in a water treatment module, apparatus and/or process.
For the interfacial polycondensation reaction between m-phenylenediamine and trimesoyl chloride, when the mixture of hydroxyl sulfonate and alcohol amine is added into the m-phenylenediamine aqueous phase solution, on one hand, the active hydroxyl contained in the hydroxyl sulfonate and the amino group of alcohol amine can react with the acyl chloride group of trimesoyl chloride, and as a capping agent of acyl chloride, the molecular weight of the polyamide oligomer at the initial stage of the polycondensation reaction can be improved, the length of the polymer chain segment of the polyamide oligomer can be increased, and the water permeability can be improved. Meanwhile, the surface of the polyamide carries more sulfonic acid groups and hydroxyl groups, so that the hydrophilicity of the polyamide layer is greatly improved, and the water flux is greatly improved. On the other hand, the polyhydroxy sulfonate can be used as a cross-linking agent to be cross-linked with acyl chloride, so that the cross-linking degree of polyamide is improved, and the desalting rate of a polyamide layer is further ensured; more importantly, after the amino group of the small molecular alcohol amine participates in the reaction in the polyamide structure, the hydroxyl group at the tail end can form a hydrogen bond structure with the sulfonic group of the hydroxyl sulfonate, so that the small molecular alcohol amine and the sulfonic group of the hydroxyl sulfonate can stably exist in the polyamide layer, and the small molecular alcohol amine and the sulfonic group have a certain synergistic effect. Therefore, by adding the blend of the hydroxyl sulfonate and the micromolecular alcohol amine into the aqueous phase solution, the hydrophilicity of the reverse osmosis membrane can be improved, and the performance of the membrane can be improved.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
1) according to the invention, the mixture of the hydroxyl sulfonate and the alcohol amine is added into the m-phenylenediamine aqueous phase solution, so that the surface hydrophilicity of the prepared reverse osmosis membrane doped with the mixture of the hydroxyl sulfonate and the alcohol amine is greatly improved, the water flux of the membrane is obviously improved, the desalination rate is almost not lost, and the excellent permeability is shown under the test pressure with lower energy consumption.
2) The preparation method of the low-energy-consumption high-flux reverse osmosis membrane has the characteristics of greenness, safety, simplicity in operation, easiness in industrial production and the like.
3) The evaluation experiments of membrane desalination rate and permeation flux and the hydrophilicity evaluation experiments show that compared with the common reverse osmosis membrane, the reverse osmosis membrane with low energy consumption and high flux prepared by the invention has the characteristics of high hydrophilicity and high water yield, and can keep higher salt removal rate, and the permeation flux can reach 45-60L/(m) under the test conditions of treating 500ppm sodium chloride brackish water and 0.69MPa which are known in the industry2H), the desalination rate of the sodium chloride can reach 99.0-99.2%, so that the method can be applied to the water treatment fields of industrial water supply, wastewater recycling and the like.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
A reverse osmosis membrane with low energy consumption and high flux comprises a polysulfone porous supporting layer and a polyamide desalting layer formed on the polysulfone porous supporting layer, wherein the inside or the surface of the polyamide desalting layer contains a blend of hydroxy sulfonate and micromolecular alcohol amine.
The polysulfone porous support layer is a polysulfone support membrane formed on a nonwoven fabric, and the polysulfone support membrane can be prepared by a technique known in the art. The polyamide desalting layer formed on the polysulfone porous supporting layer is cross-linked aromatic polyamide with a three-dimensional network structure, and is formed by performing interfacial polycondensation on an aqueous phase solution containing m-phenylenediamine and an organic phase solution containing trimesoyl chloride, and a blend of hydroxy sulfonate and micromolecular alcohol amine is added in the process of forming the polyamide desalting layer on the polysulfone porous supporting layer, so that the acyl chloride groups in the formed polyamide desalting layer are cross-linked with the blend of the hydroxy sulfonate and the micromolecular alcohol amine. The polyamide desalting layer can also be prepared by a method known in the art, such as contacting a porous support layer with an aqueous solution containing m-phenylenediamine, then contacting with an organic phase solution of trimesoyl chloride, and then performing heat treatment and rinsing to form a polyamide desalting layer on the porous support layer. It will be appreciated by those skilled in the art that the present invention is not limited to the embodiments described herein, but is to be accorded the full scope of the appended claims.
The hydroxyl sulfonate is aliphatic hydroxyl sulfonate or aromatic hydroxyl sulfonate, and can be one or more of sodium hydroxymethyl sulfonate, sodium hydroxyethyl sulfonate, sodium 3-hydroxy-1-propane sulfonate, sodium 4-hydroxybutane sulfonate, sodium p-hydroxybenzene sulfonate dihydrate, disodium 1, 4-dihydroxy-1, 4-butane sulfonate, sodium 2, 7-dihydroxy naphthalene-3, 6-disulfonate, sodium 2, 3-dihydroxy naphthalene-6-sulfonate, sodium 1, 2-dihydroxy benzene-3, 5-disulfonate and potassium 2, 5-dihydroxy benzene sulfonate; among them, the hydroxysulfonate is preferably a polyhydroxysulfonate, and may be an aliphatic polyhydroxysulfonate or an aromatic polyhydroxysulfonate, for example, 1, 4-dihydroxy-1, 4-butanedisulfonic acid disodium salt, 2, 5-dihydroxybenzenesulfonic acid potassium salt, and the like. The small molecular alcohol amine is one or more of monoethanolamine, diethanolamine, methyldiethanolamine and isopropanolamine, and is preferably isopropanolamine. The alcohol amine is only small molecular alcohol amine, so that the amino of the small molecular alcohol amine is prevented from participating in the reaction in a polyamide structure due to the steric hindrance effect of a large molecular weight or a large group. Meanwhile, the specific form of the small-molecule alcohol amine is not limited at all, and the main action of the invention is the amino and hydroxyl in the alcohol amine.
Specifically, in the preparation method of the reverse osmosis membrane with low energy consumption and high flux, the polysulfone porous supporting layer is contacted with an aqueous phase solution, the excess aqueous phase is removed, then the polysulfone porous supporting layer is contacted with an organic phase solution containing trimesoyl chloride, and then the heat treatment and the rinsing are carried out, so that the polyamide desalting layer is formed on the polysulfone porous supporting layer. Wherein in the aqueous phase solution, the mass percentage of the hydroxyl sulfonate is 0.5-2%, the mass percentage of the small molecular hydramine is 0.01-0.1%, the mass percentage of the m-phenylenediamine is 1.5-3.5%, and the balance is water; in the organic phase solution, the mass percentage of trimesoyl chloride is 0.06% -0.2% of the total mass of the organic phase solution, and the balance is organic solvent. The organic solvent is selected from one or more of aliphatic alkane, aromatic alkane and halogenated alkane, preferably from aliphatic alkane, and further preferably from at least one of isopar G, isopar L and isopar H isoalkane of Exxon Mobil. Preferably, the organic phase solution further contains a trialkyl phosphate complexing agent, preferably tributyl phosphate, and the mass fraction of the complexing agent is preferably 0.07-0.25 wt%, based on the total mass of the organic phase solution including trimesoyl chloride, the complexing agent and the solvent.
Wherein the contact time of the polysulfone porous supporting layer with the aqueous phase solution and the trimesoyl chloride organic phase solution is 10-300s, preferably 30-100s, and more preferably 30-60 s. The contact can be made by the known techniques, for example by dip coating or single-side coating, preferably by dip coating. The length of contact time has an effect on the performance of the membrane, and it will be understood by those skilled in the art that a suitable extension of the contact time will slightly reduce the water flux of the reverse osmosis membrane while the salt rejection will slightly increase, and the contact time is generally selected to be 30-60 s.
In the preparation method of the reverse osmosis membrane with low energy consumption and high flux, the heat treatment is carried out in hot air, and the specific heat treatment equipment is not limited at all, so that the prior art can be referred to. The invention only needs to control the temperature and time of heat treatment, for example, the temperature of hot air is 70-120 ℃, preferably 90-100 ℃; the heat treatment time is 2-15 min, preferably 3-6 min.
In the method for preparing the reverse osmosis membrane with low energy consumption and high flux, the rinsing can be performed by the known technology in the field, for example, the following steps can be performed: sequentially rinsing with methanol water solution and citric acid water solution for 2-5min, and finally rinsing with water. Wherein the concentration of the methanol water solution is 10.0-20.0 wt% (mass concentration), and the temperature is 40-60 ℃; the concentration of the citric acid aqueous solution is 0.5-1.0 wt% (mass concentration), and the temperature is 60-90 ℃.
On the other hand, the invention provides the application of the reverse osmosis membrane with low energy consumption and high flux or the reverse osmosis membrane with low energy consumption and high flux prepared by the preparation method in the field of water treatment. The water treatment module or apparatus may be any module or apparatus to which the polyamide reverse osmosis membrane of the present invention is attached, which can be applied to a water treatment process. The "use in a water treatment module, device and/or method" includes application to a module or device product fitted with a low energy and high flux reverse osmosis membrane of the invention, and also includes application to the preparation of such a module or device product; the components can be spiral wound membrane components, disc tube type flat membrane components and the like; the device can be used for household/commercial reverse osmosis water purifiers, industrial boiler feed water reverse osmosis water purification devices, industrial reclaimed water reuse reverse osmosis devices, seawater desalination devices and the like; the water treatment method may be, for example: bitter water waste water recycling, drinking water manufacturing, seawater desalination and the like.
The invention is further illustrated by the following more specific examples, which are given by way of illustration only and are not to be construed as limiting the invention in any way.
The raw material sources adopted in the examples of the invention and the comparative examples are shown in table 1; unless otherwise specified, all are commercially available conventional starting materials.
TABLE 1 sources of raw materials
The evaluation methods used in the examples of the present invention or the comparative examples are explained below:
1. evaluation of salt rejection and permeation flux
Salt rejection and permeate flux are two important parameters for evaluating the separation performance of reverse osmosis membranes. The invention evaluates the separation performance of the reverse osmosis membrane according to GB/T32373 and 2015 reverse osmosis membrane test method.
The salt rejection (R) is defined as: under certain operating conditions, the salt concentration (C) of the feed solutionf) With the salt concentration (C) in the permeatep) The difference is divided by the salt concentration (C) of the feed solutionf) As shown in formula (1).
Permeate flux is defined as: the volume of water per membrane area per unit time that permeates under certain operating conditions is expressed in L/(m)2·h)。
The reverse osmosis membrane performance measurement adopts the following operating conditions: the feed solution was a 500ppm aqueous sodium chloride solution, the pH of the solution was 7.0. + -. 0.5, the operating pressure was 0.69MPa, and the operating temperature was 25 ℃.
2. Hydrophilicity test
The hydrophilicity of the reverse osmosis membrane has important influence on the membrane performance, and the hydrophilicity of the reverse osmosis membrane is evaluated according to HY/T212-016 'reverse osmosis membrane hydrophilicity test method'.
Under the condition specified by the test method, a contact angle tester is adopted to drop water drops on the surface of the reverse osmosis membrane, and the hydrophilicity and the hydrophobicity of the membrane material are represented by measuring the contact angle of the water drops on the surface of the membrane. The lower the contact angle value, the more hydrophilic the membrane surface.
The invention adopts a Dataphysics OCA25 optical contact angle tester to test the contact angle of the membrane, and in order to ensure the accuracy of the analysis result, the detection is carried out for more than 5 times at different positions of the reverse osmosis membrane, and the average value is obtained. The test conditions are that the environmental temperature is 23.0 +/-2.0 ℃ and the relative humidity is 50% +/-5%.
The examples of the present invention and the comparative examples uniformly used polysulfone support membranes prepared by the following conventional methods and will not be described separately.
Preparation of polysulfone support membrane: dissolving 16.5 wt% of polysulfone resin and 10.0 wt% of ethylene glycol monomethyl ether in dimethylformamide to obtain a polysulfone membrane casting solution; then the filtered and defoamed polysulfone membrane casting solution is coated and scraped on a polyester non-woven fabric; and then the water phase is added for film formation, and the polysulfone support film is obtained after cleaning.
Example 1
The polysulfone support membrane prepared by the method is adopted, and the reverse osmosis membrane is prepared by the following method:
(1) preparing aqueous solution of 2.5 wt% of m-phenylenediamine, 1 wt% of sodium hydroxymethyl sulfonate and 0.05% of isopropanolamine, and stirring at room temperature to completely dissolve the m-phenylenediamine and the sodium hydroxymethyl sulfonate.
(2) Contacting a polysulfone support membrane with the aqueous phase solution for 30s, removing excessive water on the surface of the membrane, then contacting with an organic phase solution containing 0.15 wt% of trimesoyl chloride and 0.16 wt% of tributyl phosphate for 30s, and carrying out interfacial polycondensation to form a polyamide composite membrane; wherein the organic phase solvent is isopar G isoparaffin.
(3) Vertically draining the composite membrane in air for 1min, and treating in hot air at 100 deg.C for 6 min; then rinsing in a methanol water solution with the temperature of 50 ℃ and the concentration of 20.0 wt% and a citric acid water solution with the temperature of 60 ℃ and the concentration of 1.0 wt% for 2min respectively; and finally, rinsing the composite membrane by using deionized water to obtain the crosslinked aromatic polyamide reverse osmosis membrane. .
Examples 2 to 8
A crosslinked aromatic polyamide reverse osmosis membrane was prepared according to the method of example 1, except for the kinds and the compounding ratios of the raw materials shown in Table 2.
Comparative example 1
The polysulfone support membrane prepared by the method is adopted, and the reverse osmosis membrane is prepared by the following method:
preparing a water phase solution of m-phenylenediamine with the mass concentration of 2.5 wt%; contacting the polysulfone support membrane with the aqueous solution for 30 s; removing excessive water on the surface of the membrane, then carrying out contact reaction on the membrane and an organic phase solution containing 0.15 wt% of trimesoyl chloride and 0.16 wt% of tributyl phosphate for 30s, and carrying out interfacial polycondensation to form a polyamide composite membrane; wherein the organic phase solvent is isopar G isoparaffin. Vertically draining the composite membrane in air for 1min, and treating in hot air at 100 deg.C for 6 min; then rinsing in a methanol water solution with the temperature of 50 ℃ and the concentration of 20.0 wt% and a citric acid water solution with the temperature of 60 ℃ and the concentration of 1.0 wt% for 2min respectively; and finally, rinsing the composite membrane by using deionized water to obtain the crosslinked aromatic polyamide reverse osmosis membrane.
Comparative example 2
The polysulfone support membrane prepared by the method is adopted, and the reverse osmosis membrane is prepared by the following method:
preparing an aqueous phase solution of metaphenylene diamine with the mass concentration of 2.5 wt% and isopropanolamine with the mass concentration of 0.05%; contacting the polysulfone support membrane with the aqueous solution for 30 s; removing excessive water on the surface of the membrane, then carrying out contact reaction on the membrane and an organic phase solution containing 0.15 wt% of trimesoyl chloride and 0.16 wt% of tributyl phosphate for 30s, and carrying out interfacial polycondensation to form a polyamide composite membrane; wherein the organic phase solvent is isopar G isoparaffin. Vertically draining the composite membrane in air for 1min, and treating in hot air at 100 deg.C for 6 min; then rinsing in a methanol water solution with the temperature of 50 ℃ and the concentration of 20.0 wt% and a citric acid water solution with the temperature of 60 ℃ and the concentration of 1.0 wt% for 2min respectively; and finally, rinsing the composite membrane by using deionized water to obtain the crosslinked aromatic polyamide reverse osmosis membrane.
Comparative example 3
The polysulfone support membrane prepared by the method is adopted, and the reverse osmosis membrane is prepared by the following method:
preparing an aqueous solution of metaphenylene diamine with the mass concentration of 2.5 wt%, 1 wt% of glycol and 0.05% of isopropanolamine; contacting the polysulfone support membrane with the aqueous solution for 30 s; removing excessive water on the surface of the membrane, then carrying out contact reaction on the membrane and an organic phase solution containing 0.15 wt% of trimesoyl chloride and 0.16 wt% of tributyl phosphate for 30s, and carrying out interfacial polycondensation to form a polyamide composite membrane; wherein the organic phase solvent is isopar G isoparaffin. Vertically draining the composite membrane in air for 1min, and treating in hot air at 100 deg.C for 6 min; then rinsing in a methanol water solution with the temperature of 50 ℃ and the concentration of 20.0 wt% and a citric acid water solution with the temperature of 60 ℃ and the concentration of 1.0 wt% for 2min respectively; and finally, rinsing the composite membrane by using deionized water to obtain the crosslinked aromatic polyamide reverse osmosis membrane.
Comparative example 4
A crosslinked aromatic polyamide reverse osmosis membrane was prepared according to the method of example 1, except for the kinds and ratios of raw materials shown in Table 2.
Table 2 raw material types and ratios in examples
The salt rejection and the permeation flux of the reverse osmosis membranes prepared in the examples and comparative examples were evaluated, and the results are reported in the permeation performance of the reverse osmosis membrane in table 3. The results of the contact angle values after hydrophilicity evaluation are also reported in table 3.
TABLE 3 evaluation results of salt rejection, permeation flux, and hydrophilicity
By combining the experimental results in tables 2 and 3, the mixture of the hydroxyl sulfonate and the alcoholamine is added into the m-phenylenediamine aqueous phase solution, so that the surface hydrophilicity of the prepared reverse osmosis membrane doped with the mixture of the hydroxyl sulfonate and the alcoholamine is greatly improved, the water flux of the membrane is obviously improved, the desalting rate is almost not lost, and the excellent permeability is shown under the test pressure with low energy consumption. In example 8, two kinds of hydroxyl sulfonate and alcohol amine blend are added into 3.5% m-phenylenediamine aqueous solution, and the flux of the membrane is reduced to some extent due to the higher concentration of the added m-phenylenediamine, but the addition of the two kinds of hydroxyl sulfonate effectively improves the contact angle, and the smaller contact angle improves the hydrophilic property of the membrane.
The experimental results are shown in detail as follows: compared with the common polyamide reverse osmosis membrane of the comparative example 1, the flux of the reverse osmosis membrane is improved by about 50-100%, the salt rejection rate is basically kept unchanged, and the contact angle of the membrane is greatly reduced from 70 degrees to 20-42 degrees, which shows that the hydrophilicity is obviously improved.
Compared with the reverse osmosis membrane of the comparative example 2 without the added hydroxyl sulfonate, the reverse osmosis membrane of the invention has the advantages that the flux is improved by about 46-65%, the salt rejection rate is slightly better than that of the comparative example 2, and the contact angle of the membrane is reduced from 66 degrees to 27-42 degrees, which shows that the added hydroxyl sulfonate has obvious improvement on the hydrophilicity of the membrane.
Compared with the comparative example 3 in which glycol containing hydroxyl groups is added instead of the hydroxyl sulfonate, the flux of the reverse osmosis membrane is improved by about 20-35%, the salt rejection is better than that of the comparative example 3, the contact angle of the membrane is reduced from 59 degrees to 27-42 degrees, and the fact that the hydrophilicity, the salt rejection and the flux of the membrane are improved more obviously by adding the hydroxyl sulfonate compared with the glycol containing the hydroxyl groups is shown, because the hydrophilicity of the polyamide layer is greatly improved due to the fact that more sulfonic acid groups and hydroxyl groups are carried on the surface of the polyamide layer, and therefore the water flux is greatly improved. In addition, the polyhydroxy sulfonate can be used as a cross-linking agent to be cross-linked with acyl chloride, so that the cross-linking degree of polyamide is improved, and the desalting rate of a polyamide layer is further ensured.
Compared with comparative example 4 in which the hydroxyl sulfonate is added but the isopropanolamine is not added, the flux of the reverse osmosis membrane is improved by about 6-20%, the salt rejection rate is basically kept unchanged, the contact angle of the membrane is slightly improved, the improvement of the membrane performance by the hydroxyl sulfonate is dominant, and the hydrophilicity and the flux of the membrane are improved most obviously by the hydroxyl sulfonate and the isopropanolamine under the synergistic action. The amine group of the small molecular alcohol amine participates in the reaction in the polyamide structure, and then the hydroxyl group at the tail end can form a hydrogen bond structure with the sulfonic acid group of the hydroxyl sulfonate, so that the hydroxyl group and the sulfonic acid group can stably exist in the polyamide layer, and the amine group and the hydroxyl group have certain synergistic effect.
The evaluation experiments of membrane desalination rate and permeation flux and the hydrophilicity evaluation experiments show that compared with the common reverse osmosis membrane, the reverse osmosis membrane with low energy consumption and high flux prepared by the invention has the characteristics of high hydrophilicity and high water yield, and can keep higher salt removal rate, and the permeation flux can reach 45-60L/(m) under the test conditions of treating 500ppm sodium chloride brackish water and 0.69MPa which are known in the industry2H), the desalination rate of the sodium chloride can reach 99.0-99.2%, so the method can be applied to the water treatment fields of industrial water supply, wastewater recycling and the like.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (15)
1. A low energy consumption high flux reverse osmosis membrane, characterized in that, the reverse osmosis membrane comprises a polysulfone porous supporting layer and a polyamide desalting layer formed on the porous supporting layer, the inside or the surface of the polyamide desalting layer contains a mixture of hydroxyl sulfonate and alcohol amine;
the hydroxyl sulfonate is one or more of hydroxymethyl sodium sulfonate, hydroxyethyl sodium sulfonate, 3-hydroxy-1-propane sodium sulfonate, 4-hydroxybutane sodium sulfonate, p-hydroxy benzene sodium sulfonate dihydrate, 1, 4-dihydroxy-1, 4-butane disulfonic acid disodium salt, 2, 7-dihydroxy naphthalene-3, 6-sodium disulfonate, 2, 3-dihydroxy naphthalene-6-sodium sulfonate, 1, 2-dihydroxy benzene-3, 5-sodium disulfonate and 2, 5-dihydroxy benzene potassium sulfonate; the alcohol amine is small molecular alcohol amine;
the polyamide desalting layer is formed by performing interfacial polycondensation on m-phenylenediamine aqueous phase solution and trimesoyl chloride organic phase solution to form crosslinked aromatic polyamide with a three-dimensional network structure.
2. The low energy consumption high flux reverse osmosis membrane of claim 1, wherein the small molecule alcohol amine is one or more of monoethanolamine, diethanolamine, methyldiethanolamine, isopropanolamine.
3. The low energy consumption high flux reverse osmosis membrane of claim 2, wherein the small molecule alcohol amine is isopropanolamine.
4. The low energy consumption high flux reverse osmosis membrane of any one of claims 1-3, wherein the polysulfone porous support layer is a polysulfone support membrane formed on a non-woven fabric.
5. A method of preparing a low energy consumption high flux reverse osmosis membrane according to any one of claims 1-4 comprising the steps of:
1) dissolving m-phenylenediamine aqueous phase solution, hydroxyl sulfonate and alcohol amine blend in water;
2) after the polysulfone porous supporting layer is contacted with the aqueous phase solution, removing the redundant aqueous phase, and then contacting with the trimesoyl chloride organic phase solution;
3) performing interfacial polycondensation reaction on m-phenylenediamine and trimesoyl chloride to form a polyamide desalting layer doped with a mixture of hydroxy sulfonate and alcohol amine on the polysulfone porous supporting layer, and then performing heat treatment and rinsing to obtain the reverse osmosis membrane.
6. The preparation method of a low-energy-consumption high-flux reverse osmosis membrane according to claim 5, wherein the mass concentration of the m-phenylenediamine in the aqueous solution in the step 1) is 1.5-3.5 wt%; the mass percentage of the hydroxyl sulfonate is 0.5-2%, and the mass percentage of the alcohol amine is 0.01-0.1%.
7. The preparation method of the low-energy-consumption high-flux reverse osmosis membrane according to claim 5 or 6, wherein the mass concentration of the trimesoyl chloride organic phase solution in the step 2) is 0.06wt% to 0.2 wt%; the solvent of the organic phase solution is one or more of aliphatic alkane, aromatic alkane and halogenated alkane.
8. The method for preparing a low energy consumption high flux reverse osmosis membrane according to claim 7, wherein the solvent of the organic phase solution is aliphatic alkane.
9. The method for preparing a low-energy-consumption high-flux reverse osmosis membrane according to claim 8, wherein the solvent of the organic phase solution is one or more of isopar G, isopar L and isopar H isoparaffin.
10. The preparation method of a low-energy-consumption high-flux reverse osmosis membrane according to claim 7, wherein the trimesoyl chloride organic-phase solution further contains 0.07-0.25 wt% of tributyl phosphate based on the mass of the trimesoyl chloride organic-phase solution.
11. The method for preparing a reverse osmosis membrane with low energy consumption and large flux according to claim 5, wherein the contact time of the polysulfone porous supporting layer in the step 2) with the m-phenylenediamine aqueous phase solution and the trimesoyl chloride organic phase solution is 10-300 s.
12. The method for preparing a reverse osmosis membrane with low energy consumption and high flux according to claim 11, wherein the contact time of the polysulfone porous supporting layer in the step 2) with the m-phenylenediamine aqueous phase solution and the trimesoyl chloride organic phase solution is 30-60 s.
13. The method for preparing a low energy consumption high flux reverse osmosis membrane according to claim 11, wherein the heat treatment in step 3) is performed in hot air; the temperature of the hot air is 70-120 ℃; the heat treatment time is 2-15 min.
14. The preparation method of the low-energy-consumption high-flux reverse osmosis membrane according to claim 13, wherein the temperature of the hot air in the step 3) is 90-100 ℃; the heat treatment time is 3-6 min.
15. Use of a reverse osmosis membrane according to any one of claims 1-4 or prepared by a process according to any one of claims 5-14 in a water treatment module, device and/or process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010794089.9A CN112023726B (en) | 2020-08-10 | 2020-08-10 | Low-energy-consumption high-flux reverse osmosis membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010794089.9A CN112023726B (en) | 2020-08-10 | 2020-08-10 | Low-energy-consumption high-flux reverse osmosis membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112023726A CN112023726A (en) | 2020-12-04 |
| CN112023726B true CN112023726B (en) | 2022-07-12 |
Family
ID=73576749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010794089.9A Active CN112023726B (en) | 2020-08-10 | 2020-08-10 | Low-energy-consumption high-flux reverse osmosis membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112023726B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113338052A (en) * | 2021-08-03 | 2021-09-03 | 湖南沁森高科新材料有限公司 | Seawater desalination membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103933878A (en) * | 2014-04-25 | 2014-07-23 | 浙江理工大学 | High-flux composite reverse osmosis membrane |
| CN109289557A (en) * | 2018-11-02 | 2019-02-01 | 中国科学院过程工程研究所 | A kind of decoloration film and its preparation method and application |
| CN111330459A (en) * | 2020-03-25 | 2020-06-26 | 湖南沁森高科新材料有限公司 | Preparation method of high-flux composite reverse osmosis membrane and prepared reverse osmosis membrane |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5695304A (en) * | 1979-12-28 | 1981-08-01 | Teijin Ltd | Perm selective composite membrane and its production |
| US6913694B2 (en) * | 2001-11-06 | 2005-07-05 | Saehan Industries Incorporation | Selective membrane having a high fouling resistance |
-
2020
- 2020-08-10 CN CN202010794089.9A patent/CN112023726B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103933878A (en) * | 2014-04-25 | 2014-07-23 | 浙江理工大学 | High-flux composite reverse osmosis membrane |
| CN109289557A (en) * | 2018-11-02 | 2019-02-01 | 中国科学院过程工程研究所 | A kind of decoloration film and its preparation method and application |
| CN111330459A (en) * | 2020-03-25 | 2020-06-26 | 湖南沁森高科新材料有限公司 | Preparation method of high-flux composite reverse osmosis membrane and prepared reverse osmosis membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112023726A (en) | 2020-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Song et al. | Polysulfone/sulfonated polysulfone alloy membranes with an improved performance in processing mariculture wastewater | |
| Akbari et al. | Novel sulfonated polyamide thin-film composite nanofiltration membranes with improved water flux and anti-fouling properties | |
| CN108325389B (en) | Azlactone-based polyamide membrane and preparation method thereof | |
| JP6136266B2 (en) | Composite semipermeable membrane | |
| Lin et al. | Porous diffusion dialysis membranes for rapid acid recovery | |
| CN110917907B (en) | High-flux reverse osmosis membrane and preparation method and application thereof | |
| JP2016518982A (en) | Polyamide-based water treatment separation membrane excellent in salt removal rate and permeation flow rate characteristics and method for producing the same | |
| Hu et al. | Poly (styrene sulfonic acid) sodium modified nanofiltration membranes with improved permeability for the softening of highly concentrated seawater | |
| KR20150124952A (en) | Composite semipermeable membrane | |
| CN113856501A (en) | Composite nanofiltration membrane and preparation method and application thereof | |
| CN110756061B (en) | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof | |
| JP6642860B2 (en) | Water treatment separation membrane and method for producing the same | |
| CN108159891A (en) | A kind of N- sulfenamides based polyamide water softens loose reverse osmosis composite membrane and preparation method thereof | |
| CN104028120A (en) | Method for preparing carboxymethylcellulose sodium composite-filled polyamide nanofiltration membrane | |
| Liu et al. | A tris (hydroxymethyl) aminomethane-modified polyimide membrane with efficient organic solvent resistant performance and high separation selectivity for dye/salt separation | |
| CN108479395B (en) | Forward osmosis membrane and preparation method thereof | |
| DK201900343A1 (en) | Forward osmosis membrane obtained by using sulfonated polysulfone (sPSf) polymer and production method thereof | |
| CN107486041B (en) | Ultra-low pressure composite reverse osmosis membrane and preparation method thereof | |
| Wang et al. | Synergistic regulation of macrocyclic polyamine-based polyamide nanofiltration membranes by the interlayer and surfactant for divalent ions rejection and mono-/di-ions sieving | |
| CN112023726B (en) | Low-energy-consumption high-flux reverse osmosis membrane and preparation method and application thereof | |
| Luo et al. | Cleanable natural-sugar-alcohol-based polyester membrane for highly efficient molecular separation | |
| JP2009030024A (en) | Method for producing composite semipermeable membrane | |
| CN102210981A (en) | Method for preparing polyamide reverse osmosis composite membrane | |
| CN110773004B (en) | Large-flux reverse osmosis membrane and preparation method and application thereof | |
| CN102210982B (en) | Method for preparing polyamide reverse osmosis composite membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |